Static charge-prevented photographic light sensitive element

ABSTRACT

A static charge-prevented photographic light sensitive element using an antistatic agent in combination with a dichlorophenylphenylsulfone. The combination can reduce the surface resistivity very more than in the case where the antistatic agent is used alone.

United States Patent [1 1 Inayama et al.

[ Dec. 18, 1973 Filed: Feb. 8, 1972 Appl. No.: 224,598

Foreign Application Priority Data Feb. 8, I971 Japan 46/5062 U.S. Cl. 96/87 A, 96/67, 96/l 14.2 int. Cl G03c 1/82 Field of Search. 96/87 A, 114.2

[56] References Cited UNITED STATES PATENTS 2,461,474 2/1949 Kaszuba 96/87 A 3,457,076 7/1969 Yano et al. 96/87 A Primary ExaminerRonald H. Smith Attorney-Richard C. Sughrue et al.

[ 5 7 ABSTRACT A static charge-prevented photographic light sensitive element using an antistatic agent in combination with a dichlorophenylphenylsulfone. The combination can reduce the surface resistivity very' more than in the case where the antistatic agent is used alone.

11 Claims, No Drawings STATMI CHARGE-PREVENTIED PHOTOGRAPHIC LIGHT SENSITIVE ELEMENT BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to static charge-prevented photographic light sensitive elements. More particularly, this invention relates to employment of a dichlorophenylphenylsulfone in combination with an antistatic agent to significantly reduce the surface resistivity and thereby to impart the static charge preventing effect.

2. Description of the Prior Art In the manufacture and use of photographic films, when the films are statically charged too much an electric discharge will occur between the charged films and neighboring conductors when the fims are exposed thereto, resulting in the accident of static marks. The accident of static marks also occurs when the surface of the base is stripped from the emulsion surface upon rolling back a film.

In an attempt to prevent a photographic film from being statically charged, antistatic agents of varied types have been used heretofore. It is known that the higher the concentration of the antistatic agent is, the lower the surface resistivity becomes. Therefore, the antistatic agent is used in such an amount that the surface resistivity may become approximately from 10" to l ohms. However, when an excessive amount of an antistatic agent is used, the photographic emulsion undergoes a deteriorating influence or adhesion interference, the application of such an excessive amount of the antistatic agent being impractical in most cases.

DESCRIPTION OF THE INVENTION We have now found that the above-described various defects can be eliminated by incorporating both a dichlorophenylphenylsulfone of the invention and an antistatic agent into at least one of auxiliary layers in a photographic film, for example, an anticurl layer or antihalation layer, or by applying them onto at least one of the surfaces of said layers or of a support. Thus, the present invention provides an excellent method whereby the surface resistivity can be reduced very much more than in the case where the antistatic agent is used alone. The method of the invention is extremely effective even when carried out under low humidity and its static-charge preventing effect is not changed with the passage of time. Furthermore, the dichlorophenylphenylsulfone is inert to photographic emulsions and exerts no deteriorating influence upon the photographic properties thereof.

The dichlorophenylphenylsulfones used according to the present invention may be represented by the following general formula Examples of such compounds include 2,4- dichlorophenylphenylsulfone, 2,5-dichlorophenylphenylsulfone, 3,4-dichlorophenylphenylsulfone, and the like.

Reference will now be made to the method of synthesizing these dichlorophenylphenylsulfones.

The ci ichlorophenylphenylsulfones used according to the invention can be easily prepared by the Friedel- Craft reaction of the corresponding dichlorobenzenesulfonylchloride with benzene in the presence of iron chloride. The melting points of some dichlorophenylphenylsulfones are as follows.

M.P. 2,4-dichlorophenylphenylsuIfone 9798C 2,5-dichIorophenylphenylsufone [47C 3,4-dichlorophenylphenylsulfone C cmcrnon anionic antistatic agent ONa amphoteric antistatic agent crnc o 9 cmcmon N-CH:

HO CH2CH2OH ease Q? ,2,

When these compounds are applied to a photographic light sensitive element, they should not exert any deteriorating influence upon photographic properties such as sensitivity, fog, or gradation.

When the method of the invention is applied to the back ofa photographic film base, both of the two components of the invention may be coated on its surface by spraying with the aid of an organic solvent or by dipping the surface in a solution of the components in the organic solvent, followed, in either case, by drying. The two components of the invention may also be used together with a binder such as gelatin, polyvinyl alcohol, polycarbonate or cellulose acetate.

electrodes was made of stainless steel) and reading 1- minute value of an insulation tester (Type M V, provided by Takeda Riken Ind. Co., Ltd.). The static charge generation test was conducted by the method in which an unexposed film is placed with the back surface below on a rubber sheet, and the stack adhered by pressuring with a rubber roller and thereafter stripped to generate static marks.

The temperature-humidity conditions used for the measurement was 23 C 65 percent RH. or 23 C 25 percent R.H.

The moisture adjustment of test pieces was carried out under the above described conditions for about a half day.

EXAMPLE 1 triacetate in 92 8, by weight, of methylene chloride methanol- )12 g.

Phenol2 g.

Tetrachloroethane8 g. Ethylene chloride-85 g. Methanol5 g. The surface resistivity is shown in Table 1.

TABLE 1 Quantities, Compound oi the invention 2,5-dichlorophenylphenylsulfone. ..do...

4 5 2,5-dichloropheny1phenylsulfone 2,B-dichiorophenyiphenylsulione.

2,5-dichlorophenylphenylsuIfone..

The ratio in percent 01 the active ingredient to the binder.

percent Antistatic agent 6 Same as above 6 0 Quantities, percent 0 More than 1X10".

0 Do. 5 2X10". 5

Surface resistivity cmo 0 o 2 As is evident from the above-described Table 1, the combination of 2,5-dichlorophenylphenylsulfone with an antistatic agent can reduce the surface resistivity very much more than in the case where the antistatic agent is used alone, thereby showing an excellent synergistic effect.

EXAMPLE 2 The procedure as described in Example 1 was followed using an antistatic solution of the same formula- 5 6 tion as in Example 1 but using sodium 4. A static charge-prevented photographic light sennonylphenoxypropanesulfonate as the antistatic agent. sitive element as claimed in claim 1 wherein the sup- The surface resistivity at 25 percent R.l-l. is shown in port in the element is made of a cellulose ester, polysty- Table 2. rene, or polycarbonate.

TABLE 2 Test e e t i Quint} Surfa e numl er Compound oi the invention er-cent Antistatic agent perceri ni 10 Sodium nonylphenoxypropanesultonate- 5 1 CIOHIB 0(CH2)aSOaNa 11 2,5-d1chlorophenylphenylsulfone 5 Sameas above 0 More than 1X10". 12 .do 5 do 5 2x10".

The ratio in percent of the active ingredient to the binder.

As is evident from the above-described Table 2, the 5. A static charge-prevented photographic light senpresent combination of 2,5-dichlorophenylphenylsulsitive element as claimed in claim 4 wherein the supfone with an antistatic agent can reduce the surface report in the element is a polyethylene terephthalate film. sistivity very much more than in the case where the an- 6. A static charge-prevented photographic lighttistatic agent is used alone, thereby showing a ignifisensitive element as claimed in claim 1 wherein Said ancant static charge-preventing effect. 1 tistatic agent is a cationic antistatic agent.

Furthermore, in the above-described static-charge Static 'g -p Ph p f preventing processing a ilver chlorob 'omide photo- Sensitive element as clal med In Claim 6, wherein Said graphic emulsion f Printing use containing mo|e cationic antistatic agent IS a member selected from the percent of silver bromide was applied onto the opposite 30 group consstmg of those compounds l'sted below Surface of the fi[ mg the following formulae (I), (II), (Ill), and (IV).

In the static charge generation test, at 25 percent A R.l-l., little generation of static marks was observed (1) with the films processed according to the invention but Q remarkable generation thereof with the films not pro CHHQFNL CH3 O19 cessed in accordance with the present invention was observed.

This invention has been described in considerable de- (H) tail with particular reference to preferred embodiments 0 1E350ONH(CH2)aN (CHzhOH-NQ thereof, but it will be understood that variations and 40 H3 modifications can be effected within the spirit and (III) scope of the invention as described heremabove and as defined in the appended claims. i

We claim: g

l. A static charge-prevented photographic light seng H sitive element, which comprises a support having coated thereon, a silver halide light-sensitive emulsion (Iv) layer which is characterized by using an antistatic agent CHHQSC {L 31 in combination with a dichlorophenylphenylsulfone represented by the following general formula CH 01 Y mcmon C1 8. A static charge-prevented photographic lightsensitive element as claimed in claim 1 wherein said antistatic agent is an anionic antistatic agent.

9. A static charge-prevented photographic lightsensitive element as claimed in claim 8, wherein said 2. A static charge-prevented photographic light senanionic antistfltic agent is a member E from the group consisting of those compounds listed below havsitive element as claimed in claim 1 wherein said dichlorophenylphenylsulfone is selected from the mg mg fp-Emglai-(y) or (XL group consisting of 2,4-, 2,5- and 3,4-dichlorophenyl- (V) phenylsulfones. Cami-Q0 (CH1): 8 OiNa 3. A static charge-prevented photographic light sensitive element as claimed in claim 2 wherein said' dichlorophenylphenylsulfone is 2,5-dichlorophenylsaid antistatic agent and said dichlorophenylphenylsulfone being incorporated, in combination, into at least one auxilliary photographic layer maintained on said support.

(VI) 0 O Na g/ 12 ai r snylsi qn -mr a r, 7. s me.

7 8 (VII) N 7 (X1) cm C 7H CUH:7N CHaCOO H: Nams N 5 (XII) 111,011,011

-Q C1H2vN- .CHaCOO nr 12H2sOSOaH mcmofi (IX) C11Ha5-C ONCHzCHzS OgNa (XIII) CH;

(3H3 CnHza-CONH(CH2)I-N QH, (X) flaSOa n as SO Na (XIV) N-CH:

C12H25-C I G) 15 NCH: cmcoo 10. A static charge-prevented photographic hght- H OH OH sensitive element as claimed in claim 1 wherein said anl waw iuw l teriq,anti??? 15%? a, (XV) 11. A static charge-prevented photographic light- (B sensitive element as claimed in claim 10, wherein said 2 08 amphoteric antistatic agent is a member selected from HO CHCH,OH the group consisting of those compounds listed below CHICOOG 2 having the following formulae (Xl), (XII), xm v W l V (XIV) or V a: k 

2. A static charge-prevented photographic light sensitive element as claimed in claim 1 wherein said dichlorophenylphenylsulfone is selected from the group consisting of 2,4-, 2,5- and 3,4-dichlorophenylphenylsulfones.
 3. A static charge-prevented photographic light sensitive element as claimed in claim 2 wherein said dichlorophenylphenylsulfone is 2,5-dichlorophenylphenylsulfone.
 4. A static charge-prevented photographic light sensitive element as claimed in claim 1 wherein the support in the element is made of a cellulose ester, polystyrene, or polycarbonate.
 5. A static charge-prevented photographic light sensitive element as claimed in claim 4 wherein the support in the element is a polyethylene terephthalate film.
 6. A static charge-prevented photographic light-sensitive element as claimed in claim 1 wherein said antistatic agent is a cationic antistatic agent.
 7. A static charge-prevented photographic light-sensitive element as claimed in claim 6, wherein said cationic antistatic agent is a member selected from the group consisting of those compounds listed below having the following formulae (I), (II), (III), and (IV).
 8. A static charge-prevented photographic light-sensitive element as claimed in claim 1 wherein said antistatic agent is an anionic antistatic agent.
 9. A static charge-prevented photographic light-sensitive element as claimed in claim 8, wherein said anionic antistatic agent is a member selected from the group consisting of those compounds listed below having the formulae (V), (VI), (VII), (VIII), (IX) or (X):
 10. A static charge-prevented photographic light-sensitive element as claimed in claim 1 wherein said antistatic agent is an amphoteric antistatic agent.
 11. A static charge-prevented photographic light-sensitive element as claimed in claim 10, wherein said amphoteric antistatic agent is a member selected from the group consisting of those compounds listed below having the following formulae (XI), (XII), (XIII), (XIV) or (XV): 